Back to EveryPatent.com
| United States Patent |
5,786,318
|
|
Blokzijl
, et al.
|
July 28, 1998
|
Soil Release Polymers and detergent compositions containing them
Abstract
A water-soluble copolyester comprising units of a polyglycol or capped
polyglycol (for example, polyethylene glycol or polyethylene glycol methyl
ether), an aromatic dicarboxylic acid (for example, terephthalic acid) and
at least 30 mole % of a polyol having at least three hydroxyl groups (for
example, glycerol), but free of ethylene glycol units, is a highly
effective soil release polymer for use in detergent compositions. The
aromatic dicarboxylic acid units may include units of a sulphonated
aromatic dicarboxylic acid (for example, sulphoisophthalic acid).
| Inventors:
|
Blokzijl; Wilfried (Amsterdam, NL);
Creeth; Andrew Martin (Chester, GB);
Elmes; Alfred Roy (Wirral, GB);
Green; Andrew David (Liverpool, GB);
Hull; Michael (Gwynedd, GB);
Joule; Katrin Dagmar (Wirral, GB);
Khoshdel; Ezat (South Wirral, GB)
|
| Assignee:
|
Lever Brothers Company, Division of Conopco Inc. (New York, NY)
|
| Appl. No.:
|
666157 |
| Filed:
|
June 19, 1996 |
Foreign Application Priority Data
| Jul 06, 1995[GB] | 9513799 |
| Jul 06, 1995[GB] | 9524515 |
| Sep 04, 1995[GB] | 9518011 |
| Current U.S. Class: |
510/299; 510/421; 528/272; 528/300; 528/308; 528/308.6 |
| Intern'l Class: |
C11D 003/00; C11D 017/00; C08G 063/00; C08G 063/66 |
| Field of Search: |
510/299,421
528/272,300,308,308.6
|
References Cited
U.S. Patent Documents
| 3379548 | Apr., 1968 | Jen | 106/245.
|
| 3557039 | Jan., 1971 | McIntyre et al. | 260/29.
|
| 4132680 | Jan., 1979 | Nicol | 252/547.
|
| 5142020 | Aug., 1992 | Kud et al. | 528/272.
|
| 5489481 | Feb., 1996 | Hager et al. | 428/431.
|
| 5595681 | Jan., 1997 | Panandiker et al. | 510/299.
|
| Foreign Patent Documents |
| 0 001 305 | Apr., 1979 | EP.
| |
| 0 185 427 | Jun., 1986 | EP.
| |
| 0 241 985 | Oct., 1987 | EP.
| |
| 0 241 984 | Oct., 1987 | EP.
| |
| 0 272 033 | Jun., 1988 | EP.
| |
| 0 357 280 | Mar., 1990 | EP.
| |
| 0 442 101 | Aug., 1991 | EP.
| |
| 93133 | Dec., 1977 | PL.
| |
| 121 510 | Jan., 1984 | PL.
| |
| 1 240 713 | Jul., 1971 | GB.
| |
| 1 467 098 | Mar., 1977 | GB.
| |
Other References
Great Britain Search Report in Great Britain Patent Application No.
9513799.8.
Derwent Abstract of JP 62298437 A.
|
Primary Examiner: Shah; Mukund J.
Assistant Examiner: Coleman; Brenda
Attorney, Agent or Firm: Mitelman; Rimma
Claims
We claim:
1. A water-soluble copolymer providing soil release properties when
incorporated in a laundry detergent composition, the copolymer comprising:
(i) from 2 to 30 mole % of monomer units of poly (ethylene glycol) and/or
capped poly (ethylene glycol) having the formula I
--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (I)
and/or the formula Ia:
X--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (Ia)
wherein X is a hydrogen atom or a capping group and n is an integer;
comprising from 0 to 30 mole % of uncapped glycol and from 0 to 30 mole %
of capped glycol,
(ii) from 10 to 50 mole % of monomer units of one or more aromatic
dicarboxylic acids having the formula II
--CO--AR--CO--O-- (II)
wherein Ar is a bifunctional aromatic group, optionally including units in
which Ar is sulphonated; comprising from 20 to 50 mole % of monomer units
of an unsulphonated aromatic dicarboxylic acid and from 0 to 15 wt % of
monomer units of a sulphonated aromatic dicarboxylic acid,
(iii) from 30 to 88 mole % of monomer units of a polyol having at least 3
hydroxyl groups, having the formula III:
--CH.sub.2 --A--CH.sub.2 --O-- (III)
wherein A is a bifunctional group containing at least 1 carbon atom and at
least 1 hydroxyl group.
2. A copolymer as claimed in claim 1, consisting essentially of
(i) from 10 to 30 mole % of monomer units of the poly(ethylene glycol)
and/or capped poly(ethylene glycol) (i), comprising from 0 to 30 mole % of
uncapped glycol and from 0 to 30 mole % of capped glycol,
(ii) from 30 to 50 mole % of monomer units of unsulphonated aromatic
dicarboxylic acid (ii),
(iii) from 30 to 50 mole % of monomer units of the polyol (iii).
3. A copolymer as claimed in claim 1, wherein in the formula I X represents
a hydrogen atom or a C.sub.1-4 alkyl group.
4. A copolymer as claimed in claim 1, wherein in the formula I n is an
integer from 2 to 50.
5. A copolymer as claimed in claim 4, wherein in the formula I n is an
integer from 8 to 14.
6. A copolymer as claimed in claim 1, wherein the monomer units of the
formula III have the formula IIIa:
##STR9##
wherein R.sub.1 is H, OH or C.sub.1-4 alkyl; R.sub.2 is OH; m is an
integer from 1 to 10; and where m is greater than 1, the groups R.sub.1
and R.sub.2 need not be the same at each occurrence of the group CR.sub.1
R.sub.2.
7. A copolymer as claimed in claim 6, wherein the monomer units of the
formula IIIa have the formula IIIb:
##STR10##
wherein m has the meaning given in claim 6.
8. A copolymer as claimed in claim 6, wherein in the formula IIIb m is from
1 to 4.
9. A copolymer as claimed in claim 6, wherein the unit of the formula III
is a glycerol unit.
10. A copolymer as claimed in claim 1, wherein the monomer units (ii)
comprise terephthalate units and optionally sulphoisophthalate units.
11. A water-soluble copolymer providing soil release properties when
incorporated in a laundry detergent composition, the copolymer comprising:
(i) from 2 to 10 mole % of monomer units of poly (ethylene glycol) and/or
capped poly(ethylene glycol) having the formula I
--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (I)
and/or the formula Ia:
X--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (Ia)
wherein X is a hydrogen atom or a capping group and n is an integer;
comprising from 0 to 10 mole % of uncapped glycol and from 0 to 10 mole %
of capped glycol,
(ii) from 10 to 50 mole % of monomer units of one or more aromatic
dicarboxylic acids having the formula II
--CO--AR--CO-- (II)
wherein Ar is a bifunctional aromatic group, optionally including units in
which Ar is sulphonated; comprising from 2 to 50 mole % of monomer units
of an unsulphonated aromatic dicarboxylic acid and from 1 to 15 wt % of
monomer units of a sulphonated aromatic dicarboxylic acid,
(iii) from 50 to 88 mole % of monomer units of a polyol having at least 3
hydroxyl groups, having the formula III:
--CH.sub.2 --A--CH.sub.2 --O-- (II)
wherein A is a bifunctional group containing at least 1 carbon atom and at
least 1 hydroxyl group.
12. A water-soluble copolymer providing soil release properties when
incorporated in a laundry detergent composition, which copolymer is a
copolyester obtainable from the condensation of
(i) from 2 to 30 mole %, in total, of poly(ethylene glycol) and/or
poly(ethylene glycol) methyl ether, comprising from 0 to 30 mole % of
poly(ethylene glycol) and from 0 to 30 mole % of poly(ethylene glycol)
methyl ether;
(ii) from 10 to 50 mole % of aromatic dicarboxylic acid comprising from 2
to 50 mole % of terephthalic acid, or an alkyl or aryl ester, anhydride or
acid halide thereof and from 0 to 15 mole % of sulphoisophthalic acid, or
an alkyl or aryl ester, anhydride or acid halide thereof, and
(iii) from 30 to 88 mole % of glycerol.
13. A granular adjunct suitable for incorporation into a particulate
detergent composition, which comprises on a particulate carrier material,
a copolymer comprising:
(i) monomer units of poly (ethylene glycol) and/or capped poly (ethylene
glycol) having the formula I
--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (I)
and/or the formula Ia:
X--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (Ia)
wherein X is a hydrogen atom or a capping group and n is an integer;
(ii) monomer units of one or more aromatic dicarboxylic acids having the
formula II
--CO--AR--CO--O-- (II)
wherein Ar is a bifunctional aromatic group, optionally including units in
which Ar is sulphonated;
(iii) at least 30 mole % of monomer units of a polyol having at least 3
hydroxyl groups, having the formula III:
--CH.sub.2 --A--CH.sub.2 --O-- (III)
wherein A is a bifunctional group containing at least 1 carbon atom and at
least 1 hydroxyl group.
14. A detergent composition for washing fabrics, which comprises:
(i) from 2 to 50 wt % of an organic surfactant component comprising one or
more anionic, nonionic, cationic, amphoteric or zwitterionic surfactants,
(ii) from 0 to 80 wt % of a builder component comprising one or more
inorganic detergency builders,
(iii) a soil release component comprising an effective amount of a polymer
comprising:
(i) monomer units of poly (ethylene glycol) and/or capped poly (ethylene
glycol) having the formula I
--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (I)
and/or the formula Ia:
X--O--CH.sub.2 --CH.sub.2 --O).sub.n -- (Ia)
wherein X is a hydrogen atom or a capping group and n is an integer;
(ii) monomer units of one or more aromatic dicarboxylic acids having the
formula II
--CO--AR--CO--O-- (II)
wherein Ar is a bifunctional aromatic group, optionally including units in
which Ar is sulphonated;
(iii) at least 30 mole % of monomer units of a polyol having at least 3
hydroxyl groups, having the formula III:
--CH.sub.2 --A--CH.sub.2 --O-- (III)
wherein A is a bifunctional group containing at least 1 carbon atom and at
least 1 hydroxyl group;
(iv) optionally other ingredients to 100 wt %,
all percentages being based on the detergent composition.
15. A detergent composition as claimed in claim 14, which comprises from
0.02 to 10 wt % of the copolymer.
16. A detergent composition as claimed in claim 14, which comprises from
0.1 to 3 wt % of the copolymer.
Description
TECHNICAL AREA
The present invention relates to novel copolymers exhibiting improved soil
release properties, and to their use in detergent compositions for washing
fabrics.
BACKGROUND AND PRIOR ART
Polyesters of terephthalic and other aromatic dicarboxylic acids having
soil release properties are widely disclosed in the art, in particular,
the so-called PET/POET (polyethylene terephthalate/polyoxyethylene
terephthalate) and PET/PEG (polyethylene terephthalate/polyethylene
glycol) polymers which are disclosed, for example, in U.S. Pat. No.
3,557,039 (ICI), GB 1 467 098 and EP 1305A (Procter & Gamble). Polymers of
this type are available commercially, for example, as Permalose, Aquaperle
and Milease (Trade Marks) (ICI) and Repel-O-Tex (Trade Mark) SRP3
(Rhone-Poulenc). Other patent publications disclosing soil release
polymers which are condensation products of aromatic dicarboxylic acids
and dihydric alcohols include EP 185 427A, EP 241 984A, EP 241 985A and EP
272 033A (Procter & Gamble).
The so-called PET/POET polymers have been found to enhance the oily and
particulate soil detergency obtained from organic surfactant systems,
especially on polyester and other synthetic fabrics: they are less
effective on cotton, much larger quantities of polymer being required
before an effect is observed. Certain deficiencies have also been found in
terms of water solubility and, especially for particulate detergents use,
processability.
EP 357 280A (Procter & Gamble) discloses sulphonated end-capped linear
terephthalate oligomers which are condensation products of a low molecular
weight diol, preferably propylene glycol or ethylene glycol, with
terephthalic acid. These products are stated to have substantially linear
backbones, and do not include branching or crosslinking tri- or polyvalent
monomer groups such as tri-, tetra- or polycarboxylic acid monomer groups
or tri-, tetra- or polyhydric alcohol monomer groups.
EP 442 101B (BASF) discloses soil release polymers intended for use in
liquid detergent compositions having low water content. The polymers are
obtainable by condensation of carboxylic acids containing at least two
carboxyl groups, for example, terephthalic acid; glycerol,
pentaerythritol, oligoglycerol or similar compounds; and long chain
(C.sub.8-24) alcohols, alkylphenols or alkylamines condensed with 5-80,
preferably 25 or 50, moles of ethylene oxide. The presence of long
hydrophobic chains confers on the polymers compatibility with liquid
detergent compositions by allowing them to associate with surfactant
mesophases. However, because of their greater hydrophobicity these
polymers will generally exhibit lower solubility in water than the
PET/POET and PET/PEG polymers mentioned previously.
PL 93 133B and PL 121 510B (Blachownia) disclose a fabric finishing agent
that produces a soil- and crease-resistant finish on polyester and
polyester/cellulose fabrics, which is a modified polyester prepared by
transesterifying terephthalic acid dimethyl ester (1 mole) with ethylene
glycol (2.0-3.0 moles), glycerol (0.3-0.5 mole) and polyethylene glycol of
average molecular weight about 1540 (0.15-0.4 mole). The polyester is not
water-soluble and is used in the form of a 15-20 wt % aqueous dispersion.
The present inventors have now identified a novel class of water-soluble
copolymers based on dicarboxylic acids and polyols which provide effective
soil release on both polyester and cotton fabrics, and which are also
effective in reducing soil redeposition in the wash. The polymers are
suitable for incorporation into detergent compositions of all physical
types, for example, liquids, particulates (powders), and bars.
DEFINITION OF THE INVENTION
The present invention accordingly provides a water-soluble copolymer
providing soil release properties when incorporated in a laundry detergent
composition, the copolymer comprising:
(i) monomer units of poly(ethylene glycol) and/or capped poly(ethylene
glycol) having the formula I
--O--(CH.sub.2 --CH.sub.2 O).sub.n -- (I)
and/or the formula Ia:
X--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (Ia)
wherein X is a hydrogen atom or a capping group, preferably a C.sub.1-4
alkyl group, and n is an integer;
(ii) monomer units of one or more aromatic dicarboxylic acids having the
formula II
--CO--Ar--CO--O-- (II)
wherein Ar is a bifunctional aromatic group, optionally including units in
which Ar is sulphonated; and
(iii) at least 30 mole % of monomer units of a polyol having at least 3
hydroxyl groups, having the formula III:
--CH.sub.2 --A--CH.sub.2 --O-- (III)
wherein A is a bifunctional group containing at least 1 carbon atom and at
least 1 hydroxyl group.
The invention also provides a granular adjunct suitable for incorporation
into a particulate detergent composition, which comprises a copolymer as
defined above on a particulate carrier material.
The invention further provides a detergent composition for washing fabrics,
comprising one or more organic surfactants, optionally one or more
detergency builders, and a soil release effective amount of a copolymer as
defined above, the composition preferably comprising
(i) from 2 to 50 wt % of an organic surfactant component comprising one or
more anionic, nonionic, cationic, amphoteric or zwitterionic surfactants,
(ii) from 0 to 80 wt % of a builder component comprising one or more
inorganic or organic detergency builders,
(iii) a soil release component comprising an effective amount, preferably
from 0.02 to 10 wt % and more preferably from 0.1 to 3 wt %, of a
copolymer as defined above, and
(iv) optionally other ingredients to 100 wt %, all percentages being based
on the detergent composition.
DETAILED DESCRIPTION OF THE INVENTION
The Polymers
Unlike the prior art PET/POET and similar polymers, the copolymers of the
invention do not contain ethylene glycol units. They contain a substantial
proportion (at least 30 mole %) of units of a tri- or polyhydric alcohol,
preferably glycerol, but surprisingly the crosslinking and insolubility
that would be expected does not occur. Instead, the presence of additional
hydroxyl groups appears to increase water-solubility, since the polymers
of the invention exhibit higher water-solubility than commercially
available PET/POET polymers.
The polymers are therefore more weight effective and can be used in smaller
quantities in detergent compositions.
Furthermore, the rate of dissolution and delivery of benefits into the wash
is greater than that of prior art polymers, which is especially beneficial
for use in short-wash-time machine washing.
In addition, the polymers of the invention may readily be combined with
suitable carrier materials, notably inorganic salts, to provide stable
heat-insensitive fast-dissolving granules suitable for incorporation into
particulate detergent compositions.
The water-soluble copolymers of the invention are obtainable from the
condensation of a monomer mixture comprising:
(i) poly(ethylene glycol) and/or capped poly(ethylene glycol) having the
formula I'
X--O--(CH.sub.2 --CH.sub.2 --O).sub.n --H (I')
wherein X and n have the meanings given previously,
(ii) one or more aromatic dicarboxylic acids or derivatives thereof having
the formula II'
M--CO--Ar--CO--M (II')
wherein Ar has the meaning given previously, and M and M', which may be the
same or different, each represents a leaving group, for example, a
hydroxyl group, an alkyloxy or aryloxy group or an acid halide group, or M
and M' together represent an acid anhydride group; and the aromatic
dicarboxylic acids or derivatives thereof of the formula II' may
optionally include sulphonated dicarboxylic acids or their derivatives;
(iii) at least 30 mole % of a polyol having at least 3 hydroxyl groups,
having the formula III':
HO--CH.sub.2 --A--CH.sub.2 --OH (III')
wherein A has the meaning given previously.
In the formulae I and I', X represents a hydrogen atom, or a capping group.
A preferred capping group is a C.sub.1-4 alkyl group, most preferably a
methyl group. Alternative capping groups, either uncharged or charged, as
described in the literature, are also possible.
In the formulae I and I', the value of n may suitably range from 2 to 50,
more preferably from 6 to 30 and most preferably from 8 to 14.
These ranges correspond to an approximate molecular weight of the
polytethylene glycol) monomer (calculated as the uncapped material) of
from 88 to 2200, preferably from 264 to 1320 and most preferably from 352
to 616.
Poly(ethylene glycol) of lower molecular weight (n=14 and below) is
especially preferred because the resulting polymers are biodegradable.
If desired, there may also be present minor amounts of units derived from
poly(propylene glycol) or capped poly(propylene glycol).
Preferably, the monomer units of the formula III have the formula IIIa:
##STR1##
wherein R.sub.1 is H, OH or C.sub.1-4 alkyl; R.sub.2 is OH; m is an
integer from 1 to 10; and where m is greater than 1, the groups R.sub.1
and R.sub.2 need not be the same at each occurrence of the group CR.sub.1
R.sub.2.
More preferably, the monomer units have the formula IIIb:
##STR2##
wherein m has the meaning given previously, and is preferably from 1 to 4,
and more preferably is 1 or 2.
Preferred monomer units of the formula III are glycerol units or reduced
monosaccharide units. Especially preferred monomer units of the formula
IIIb are glyceryl (m=1) or threityl (m=2) moeities. The most preferred
polyol monomer is glycerol.
Thus, the monomer units III are preferably obtainable from a polyol of the
formula IIIa'
##STR3##
wherein R.sub.1, R.sub.2 and m have the meanings given previously.
More preferably, the monomer units III are obtainable from a polyol of the
formula IIIb':
##STR4##
m preferably being from 1 to 4 and more preferably 1 or 2 as previously
indicated.
As previously indicated, preferred polyols of the formula III' are glycerol
or reduced monosaccharides. Especially preferred polyols of the formula
IIIb' are glycerol (m=1) or threitol (m=2), more especially glycerol.
In the aromatic dicarboxylic acid (ii), suitable Ar groups and aromatic
dicarboxylic groups include the following:
______________________________________
terephthalate
isophthalate
1,4-phenoxymethylene
CH.sub.2OC.sub.6 H.sub.4OCH.sub.2
4,4'-bisphenylene
C.sub.6 H.sub.4C.sub.6 H.sub.4
2,2'-diphenylpropane
##STR5##
4,4'-diphenylene oxide
C.sub.6 H.sub.4OC.sub.6 H.sub.4
sulphoisophthalate
4,4'-diphenylsulphone
##STR6##
______________________________________
The most preferred unsulphonated dicarboxylic monomer is terephthalic acid,
ie Ar is a 1,4-phenylene group --C.sub.6 H.sub.4 -- optionally in
combination with isophthalic acid, generally in a minor amount.
As previously indicated polymers containing units of both unsulphonated and
sulphonated monomers are also of great interest. The presence of an
unsulphonated monomer is essential, while the presence of a sulphonated
monomer is optional. The preferred combination is terephthalic acid,
optionally plus isophthalic acid, and sulphoisophthalic acid.
Optional Aliphatic Dicarboxylic Monomer
If desired, the monomer mixture may additionally contain a minor amount,
for example, from 0.2 to 10 mole %, preferably from 0.5 to 5 mole % and
more preferably from 0.5 to 2 mole %, of an aliphatic dicarboxylic acid
monomer, in order to increase hydrophobicity and reduce glass transition
temperature. Preferred aliphatic monomers are C.sub.4 -C.sub.10
dicarboxylic acids or derivatives thereof, acids having an even number of
carbon atoms being especially preferred in order to optimise chain
packing. An example of a suitable monomer is dimethyl adipate, providing
adipic acid units in the polymer.
Monomer Ratios
Monomer ratios may vary widely provided that the mole percentage of units
of the polyol (iii) is at least 30 mole %.
Preferred polymers consist essentially of:
(i) from 2 to 30 mole % of monomer units of the poly(ethylene glycol)
and/or capped poly(ethylene glycol) (i), comprising from 0 to 30 mole % of
uncapped glycol and from 0 to 30 mole % of capped glycol,
(ii) from 10 to 50 mole % of monomer units of the aromatic dicarboxylic
acid (ii), comprising from 2 to 50 mole % of monomer units of an
unsulphonated aromatic dicarboxylic acid and from 0 to 15 wt % of monomer
units of a sulphonated aromatic dicarboxylic acid,
(iii) from 30 to 88 mole % of monomer units of the polyol (iii).
Especially preferred unsulphonated polymers of the invention consist
essentially of:
(i) from 10 to 30 mole % of monomer units of the poly(ethylene glycol)
and/or capped poly(ethylene glycol) (i), comprising from 0 to 30 mole % of
uncapped glycol and from 0 to 30 mole % of capped glycol,
(ii) from 30 to 50 mole % of monomer units of the aromatic dicarboxylic
acid (ii),
(iii) from 30 to 50 mole % of monomer units of the polyol (iii).
Especially preferred sulphonated polymers of the invention consist
essentially of:
(i) from 2 to 10 mole % of monomer units of the poly(ethylene glycol)
and/or capped poly(ethylene glycol) (i), comprising from 0 to 10 mole % of
uncapped glycol and from 0 to 10 mole % of capped glycol,
(ii) from 10 to 50 mole % of monomer units of the aromatic dicarboxylic
acid (ii), comprising from 2 to 50 mole % of monomer units of an
unsulphonated aromatic dicarboxylic acid and from 1 to 15 wt % of monomer
units of a sulphonated aromatic dicarboxylic acid,
(iii) from 50 to 88 mole % of monomer units of the polyol (iii).
Thus broadly preferred copolymers of the invention are obtainable from the
condensation of a monomer mixture consisting essentially of:
(i) from 2 to 30 mole % of the poly(ethylene glycol) and/or capped
poly(ethylene glycol) (i), comprising from 0 to 30 mole % of uncapped
glycol and from 0 to 30 mole % of capped glycol,
(ii) from 10 to 50 mole % of the aromatic dicarboxylic acid (ii),
comprising from 2 to 50 mole % of an unsulphonated aromatic dicarboxylic
acid and from 0 to 15 wt % of a sulphonated aromatic dicarboxylic acid,
(iii) from 30 to 88 mole % of the polyol (iii).
Unsulphonated copolymers of the invention are preferably obtainable from
the condensation of a monomer mixture consisting essentially of
(i) from 10 to 30 mole % of the poly(ethylene glycol) and/or capped
poly(ethylene glycol) (i), comprising from 0 to 30 mole % of uncapped
glycol and from 0 to 30 mole % of capped glycol,
(ii) from 30 to 50 mole % of an unsulphonated aromatic dicarboxylic acid
(ii),
(iii) from 30 to 50 mole % of the polyol (iii).
Sulphonated copolymers of the invention are preferably obtainable from the
condensation of a monomer mixture consisting essentially of
(i) from 2 to 10 mole % of monomer units of the poly(ethylene glycol)
and/or capped poly(ethylene glycol) (i), comprising from 0 to 10 mole % of
uncapped glycol and from 0 to 10 mole % of capped glycol,
(ii) from 10 to 50 mole % of monomer units of the aromatic dicarboxylic
acid (ii), comprising from 2 to 50 mole % of monomer units of an
unsulphonated aromatic dicarboxylic acid and from 1 to 15 wt % of monomer
units of a sulphonated aromatic dicarboxylic acid,
(iii) from 50 to 88 mole % of monomer units of the polyol (iii).
Preferred Polymers
In preferred copolymers of the invention, the following combinations of
monomer units may, for example, be present:
(i) units of the formula A:
--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (A)
at least in part present in the form of end units of the formula A':
X--O--(CH.sub.2 --CH.sub.2 --O).sub.n -- (A')
wherein X is a hydrogen atom or a capping group, preferably a C.sub.1-4
alkyl group and more preferably a methyl group, and
(ii) units of the formula C:
##STR7##
wherein p is from 1 to 50, preferably from 1 to 10; or units of the
formula C':
##STR8##
(iii) units of the formula B:
--›--CO--Ar--CO--O--(CH.sub.2 --CH.sub.2 --O--).sub.a !.sub.t (B)
wherein t is from 1 to 50, preferably from 1 to 10; optionally present in
part as end units of the formula B':
HO--›(O--CH.sub.2 --CH.sub.2 --).sub.q --O--CO--Ar--CO--!.sub.z --(B')
wherein z is from 1 to 50, preferably from 1 to 10.
Typical values of n, a and q are from 2 to 50, preferably from 6 to 30, and
especially from 8 to 14.
The units A and A' are preferably poly(ethylene glycol) moieties, also
known as poly(ethylene oxide) or poly(ethyleneoxy) moieties. Optionally
corresponding units derived from poly(propylene glycol) may additionally
be present. The end units A' are are optionally end-capped with a
C.sub.1-4 alkyl group, preferably a methyl group. Thus preferred units A'
are derived from poly(ethylene glycol methyl ether) ("methyl PEG").
The units C and C' are units of an ester of the aromatic dicarboxylic acid
or acids (preferably terephthalic acid, optionally plus sulphoisophthalic
acid) with the C.sub.3-12 polyol (preferably glycerol or threitol). Thus
preferred units C are poly(glyceryl terephthalate) (PGT) units and
poly(threityl terephthalate) (PTT) units.
The units B and B' are units of an ester of poly(ethylene glycol) with the
aromatic dicarboxylic acid (preferably terephthalic acid, optionally plus
isophthalic acid and/or sulphoisophthalic acid). Thus preferred units B
and B' are poly(ethylene glycol terephthalate) (POET) units.
Unlike the PET/POET polymers of the prior art, the polymers of the
invention do not contain poly (ethylene terephthalate) (PET) units, or
corresponding units derived from other aromatic dicarboxylic acids; that
is to say, the monomers from which they are derived do not include
ethylene glycol.
There are three especially preferred classes of polymer within the scope of
the present invention:
(i) A'--B--C--A' type end-capped polyesters;
(ii) A'--C--A' type end-capped polyesters;
(iii) B'--C' type uncapped copolyesters.
Molecular Weights
Preferred polymers for use in liquid and particulate detergent compositions
have molecular weights within the range of from 200 to 20 000, preferably
from 300 to 10 000 and desirably from 400 to 5000.
Water Solubility and Rate of Dissolution
The polymers of the invention are highly water-soluble. Unlike the
Permalose (Trade Mark) polymers of the prior art, they do not contain the
long ethylene terephthalate blocks which produce material of low water
solubility, thus reducing the overall solubility of the polymer. The
Permalose polymers have the further disadvantage that at high temperatures
the less water-soluble material tends to take up the more water-soluble
material, so that overall solubility is further reduced by high
temperature processing as may be needed, for example, when preparing
detergent powders. This does not occur with the polymers of the invention
which are highly water-soluble both at ambient temperatures and at
elevated temperatures.
As previously indicated, the polymers of the invention also exhibit a
substantially greater rate of dissolution in water than do known soil
release copolyesters.
Without wishing to be bound by theory, we believe these advantageous
properties may be attributed to the greater hydrophilicity of the polymers
of the invention, compared with PET/POET polymers, due to the presence of
free (secondary) hydroxyl groups.
Surprisingly, the presence of free (secondary) hydroxyl groups in the
polyol monomer does not result in crosslinking to give insoluble material.
Preferred polymers of the invention are substantially linear. However,
polymers containing some degree of branching are within the scope of the
invention.
Preparation of the Polymers
The polymers of the invention may be prepared by condensation of
(i)(a) an end-capped poly(ethylene glycol) and/or
(i)(b) poly(ethylene glycol),
(ii) the aromatic dicarboxylic acid HOOC--Ar--COOH or a suitable derivative
(C.sub.1-4 alkyl ester, acid halide, anhydride);
(iii) the chosen polyol in an amount of at least 30 mole %.
If the dicarboxylic acid is used in alkyl ester form, the reaction is
suitably carried out in the presence of a base catalyst, at an elevated
temperature, for example, 120.degree.-180.degree. C., and, if desired,
under reduced pressure. The lower alcohol (normally methanol) generated
during the reaction is distilled off.
Suitable catalysts include alkyl and alkaline earth metals, for example,
lithium, sodium, calcium and magnesium, as well as transition and Group
IIB metals, for example, antimony, manganese, cobalt and zinc, usually as
oxides, carbonates or acetates. A preferred catalyst comprises antimony
trioxide and calcium acetate.
The esters and oligomers produced in the condensation (ester interchange)
reaction may then be polymerised to the desired molecular weight, by
raising the temperature further, typically to 180.degree.-250.degree. C.
The degree of polymerisation may be monitored by gel permeation
chromatography, NMR, and end-group titrations. Where other derivatives of
the aromatic dicarboxylic acid are used as starting materials, other
catalysts and reaction conditions may be appropriate.
Granules or Adjuncts
As previously indicated, the polymers of the invention may readily be
combined with a suitable carrier material to form free-flowing heat-stable
granules or adjuncts suitable for incorporation in, or admixture to,
particulate detergent compositions.
Suitable carrier materials are inorganic salts. Inert salts such as sodium
sulphate are preferred.
Deterrent Compositions
The copolymers of the present invention are suitable for incorporation into
detergent compositions of all physical forms, for example, liquids,
powders, gels, tablets and bars.
The polymers are suitably incorporated into detergent 4 compositions in
amounts of from 0.02 to 10 wt %, preferably from 0.1 to 3 wt %.
As previously indicated, for use in particulate detergent compositions the
polymers of the invention may suitably be in granule or adjunct form.
Detergent compositions will generally contain detergent-active compounds
and detergency builders, and may optionally contain bleaching components
and other active ingredients to enhance performance and properties.
The detergent compositions of the invention will contain, as essential
ingredients, one or more detergent-active compounds (surfactants) which
may be chosen from soap and non-soap anionic, cationic, nonionic,
amphoteric and zwitterionic detergent-active compounds, and mixtures
thereof. Many suitable detergent-active compounds are available and are
fully described in the literature, for example, in "Surface-Active Agents
and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds that can be used are soaps and
synthetic non-soap anionic and nonionic compounds. The total amount of
surfactant present may suitably range from 5 to 40 wt %.
Anionic surfactants are well-known to those skilled in the art. Examples
include alkylbenzene sulphbnates, particularly linear alkylbenzene
sulphonates having an alkyl chain length of C.sub.8 -C.sub.15 ; primary
and secondary alkylsulphates, particularly C.sub.8 -C.sub.15 primary alkyl
sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene
sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
The polymers of the present invention are especially suitable for use in
compositions containing anionic sulphonate and sulphate type surfactants,
for example, primary alkyl sulphates, alkyl ether sulphates, alkylbenzene
sulphonates, and mixtures of these.
Nonionic surfactants that may be used include the primary and secondary
alcohol ethoxylates, especially the C.sub.8 -C.sub.20 aliphatic alcohols
ethoxylated with an average of from 1 to 20 moles of ethylene oxide per
mole of alcohol, and more especially the C.sub.10 -C.sub.15 primary and
secondary aliphatic alcohols ethoxylated with an average of from 1 to 10
moles of ethylene oxide per mole of alcohol.
Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol
monoethers, and polyhydroxyamides (glucamide).
Especially preferred are ethoxylated nonionic surfactants,
alkylpolyglycosides, and mixtures of these.
As well as the non-soap surfactants listed above, detergent compositions of
the invention may also advantageously contain fatty acid soap.
The detergent compositions of the invention will generally also contain one
or more detergency builders. The total amount of detergency builder in the
compositions will suitably range from 5 to 80 wt %, preferably from 10 to
60 wt %.
Inorganic builders that may be present include sodium carbonate, if desired
in combination with a crystallisation seed for calcium carbonate, as
disclosed in GB 1 437 950 (Unilever); crystalline and amorphous
aluminosilicates, for example, zeolites as disclosed in GB 1 473 201
(Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel)
and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470
250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B
(Hoechst). Inorganic phosphate builders, for example, sodium
orthophosphate, pyrophosphate and tripolyphosphate, may also be present,
but on environmental grounds those are no longer preferred.
The detergent compositions of the invention preferably contain an alkali
metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates
may generally be incorporated in amounts of from 10 to 70% by weight
(anhydrous basis), preferably from 25 to 50 wt %.
The zeolite may be the commercially available zeolite 4A now widely used in
laundry detergent powders. Other zeolites that may be used include
zeolites X and Y.
However, according to a preferred embodiment of the invention, the zeolite
builder incorporated in the compositions of the invention is maximum
aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A
(Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of
the zeolite P type having a silicon to aluminium ratio not exceeding 1.33.
Especially preferred is zeolite MAP having a silicon to aluminium ratio
not exceeding 1.07, more preferably about 1.00. The calcium binding
capacity of zeolite MAP is generally at least 150 mg CaO per g of
anhydrous material.
Organic builders that may be present include polycarboxylate polymers such
as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates;
monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates,
glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates,
carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates,
alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid
salts. This list is not intended to be exhaustive.
Detergent compositions according to the invention may also suitably contain
a bleach system, which may contain peroxy bleach compounds, for example,
inorganic persalts or organic peroxyacids, capable of yielding hydrogen
peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as urea
peroxide, and inorganic persalts such as the alkali metal perborates,
percarbonates, perphosphates, persilicates and persulphates.
Preferred inorganic persalts are sodium perborate monohydrate and
tetrahydrate, and sodium percarbonate. The peroxy bleach compound is
suitably present in an amount of from 5 to 35 wt %, preferably from 10 to
25 wt %.
The peroxy bleach compound may be used in conjunction with a bleach
activator (bleach precursor) to improve bleaching action at low wash
temperatures. The bleach precursor is suitably present in an amount of
from 1 to 8 wt %, preferably from 2 to 5 wt %.
A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable
bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the
polyphosphonates such as Dequest (Trade Mark), EDTMP.
Other materials that may be present in detergent compositions of the
invention include inorganic salts such as sodium carbonate, sodium
sulphate or sodium silicate; antiredeposition agents such as cellulosic
polymers; fluorescers; anti-dye-transfer polymers such as polyvinyl
pyrrolidone; inorganic salts such as sodium sulphate; lather control
agents or lather boosters as appropriate; detergent enzymes (protease,
lipase, cellulase, amylase); dyes; coloured speckles; perfumes; foam
controllers; and fabric softening compounds. This list is not intended to
be exhaustive.
EXAMPLES
The invention is further illustrated by the following non-limiting
Examples, in which parts and percentages are by weight unless otherwise
stated.
EXAMPLES 1 to 5
Preparation of Polymers
Example 1
Preparation of capped copolymer of poly(ethylene glycol methyl ether),
poly(ethylene glycol), terephthalic acid and glycerol
______________________________________
Reactants g mole mole %
______________________________________
Poly(ethylene glycol methyl ether)
30.0 0.015 4.22
(MW 2000)
Poly(ethylene glycol) (MW 1500)
60.0 0.04 11.27
Dimethyl terephthalate
25.6 0.13 36.62
Glycerol 15.5 0.17 47.89
Antimony trioxide 0.7
Calcium acetate 0.7
2,6-di-tert-butyl-methylphenol (BHT)
0.1
______________________________________
The above ingredients were charged into a flanged reactor flask provided
with bladed stirrer, thermometer to register the reactant temperature,
O-spot nitrogen inlet, and Claisen still-head with condenser for the
distillation of methanol. The temperature was first raised to
150.degree.-160.degree. C. (pot temperature) to melt the solid reactants
and thoroughly disperse the catalyst. The temperature was then raised to
175.degree. C. and held for 22 hours, before increasing it further to
200.degree. C. and holding an additional 11 hours. Much dimethyl
terephthalate sublimed onto the cooler upper part of the reactor wall
during this stronger heating period. This was periodically remelted back
into the reaction. Approximately 25% of the theoretical amount of methanol
distilled up to this stage.
While still molten, the somewhat cooled reaction mixture was transferred to
a Kugelrohr bulb, then reheated to 200.degree. C. at 0.1 torr vacuum. This
temperature was held for 1 hour to `complete` the polycondensation. The
total amount of methanol collected indicated a conversion of approximately
80%.
The polyester thus obtained was a waxy solid, melting at
35.degree.-45.degree. C. to a clear liquid. At 1% in water it gave a
reversible cloud temperature of 62.degree.-63.degree. C. Its apparent
molecular weight by GPC (THF) vs polystyrene standards was M.sub.n 5600,
M.sub.w 11000. The .sup.1 H NMR spectrum (CDCl.sub.3) showed major peaks
centred at 8.1 and 3.6 ppm assignable to terephthalate Ar--H's and
ethyleneoxy respectively. A smaller singlet at 3.4 ppm correlated with the
presence of methoxyl groups.
Example 1a
A polymer having molecular weights of M.sub.n =2750, M.sub.w 4800 was
prepared from the same reactants, in the same quantities, by a process as
described in Example 1. Its cloud point was 61.degree. C., and its
--(--EO--).sub.n -- to Ar--H ratio was 17:1.
Example 1b
A polymer having molecular weights of M.sub.n =2600, M.sub.w =4600 was
prepared from the same reactants, in the same quantities, by a process as
described in Example 1. Its cloud point was 61.degree.-62.degree. C., and
its --(--EO--).sub.n -- to Ar--H-- ratio was 20:1.
Example 2
Preparation of capped copolymer of poly(ethylene glycol methyl ether),
terephthalic acid and glycerol
______________________________________
Reactants g mole mole %
______________________________________
Poly(ethylene glycol methyl ether)
44.0 0.08 24.24
MW 550
Dimethyl terephthalate
21.6 0.11 33.33
Glycerol 12.5 0.14 42.42
Antimony trioxide 0.2
Calcium acetate 0.2
BHT 0.005
______________________________________
The preparation was carried out as in Example 1. Approximately 10% of
unreacted dimethyl terephthalate was distilled off at the Kugelrohr step,
indicating conversion of approximately 90%. The oligomeric product was a
brown viscous liquid. At 1% in water, it gave a reversible cloud point of
54.degree. C. Its molecular weight by GPC in THF was M.sub.n 1550, M.sub.w
2900. The .sup.1 H NMR spectrum (CDCl.sub.3) was generally similar to that
of the polymer of Example 1, except that the --(--EO--).sub.n -- to Ar--H
ratio was 11:1.
Example 2a
A polymer was prepared from the same reactants on a larger scale, as shown
below, by a process as described in Example 2.
______________________________________
Monomer mole mole %
______________________________________
Poly(ethylene glycol methyl ether)
0.16 24.24
MW 550
Dimethyl terephthalate
0.22 33.33
Glycerol 0.28 42.42
______________________________________
The molecular weights were M.sub.n =930, M.sub.w =1450.
The cloud point was 29.degree. C., and the --(--EO--).sub.n -- to Ar--H
ratio was 10:1.
Example 2b
A polymer was prepared from the same reactants, in the quantities used in
Example 2a, by a process as described in Example 2.
The molecular weights were M.sub.n =1600, M.sub.w =2900. The cloud point
was 56.degree. C., and the --(--EO--).sub.n -- to Ar--H ratio was 8:1.
Example 3
Preparation of capped copolymer of poly(ethylene glycol methyl ether),
terephthalic acid, and threitol
A polymer was prepared by the method of Example 2, but the glycerol was
replaced by an equivalent amount of D,L-threitol. The polymer had a
molecular weight (M.sub.w) of 2200.
Example 3a
Preparation of capped copolymer of poly(ethylene glycol methyl ether),
terephthalic acid, and sorbitol
A polymer was prepared by the method of Example 2, from the following
monomers:
______________________________________
Monomer Mole Mole %
______________________________________
Poly(ethylene glycol)
0.03 27.27
methyl ether (MW 550)
Dimethyl terephthalate
0.04 36.36
Sorbitol 0.04 36.36
______________________________________
The molecular weights were Mn=1300, Mw=2200, and the --(--EO--).sub.n -- to
Ar--H ratio was 11:1.
Example 4
Preparation of uncapped copolymer of poly(ethylene glycol), terephthalic
acid and glycerol
An uncapped polymer was prepared by the method of Example 1, the reactants
being polyethylene glycol, terephthalic acid and glycerol in the following
amounts and proportions:
______________________________________
Monomer mole mole %
______________________________________
Poly(ethylene glycol) MW 600
0.105 25.30
Dimethyl terephthalate
0.15 36.15
Glycerol 0.16 38.55
______________________________________
The polymer had molecular weights M.sub.n =1700, M.sub.w =3200. Its
--(--EO--).sub.n -- to Ar--H ratio was 9:1.
Example 4a
A polymer was prepared by a process as described in Example 4, the
reactants being polyethylene glycol, terephthalic acid and glycerol in the
following amounts and proportions:
______________________________________
Monomer mole mole %
______________________________________
Poly(ethylene glycol) MW 600
0.27 25.71
Dimethyl terephthalate
0.38 36.19
Glycerol 0.40 38.10
______________________________________
The molecular weights were M.sub.n =1600, M.sub.w =2850. The
--(--EO--).sub.n -- to Ar--H ratio was 9:1.
Example 4b
A polymer was prepared by a process as described in Example 4, the
reactants being polyethylene glycol, terephthalic acid and glycerol in the
following amounts and proportions:
______________________________________
Monomer mole mole %
______________________________________
Poly(ethylene glycol) MW 600
0.03 25.64
Dimethyl terephthalate
0.042 35.90
Glycerol 0.045 38.46
______________________________________
The molecular weights were M.sub.n =2000, M.sub.w =4250. The
--(--EO--).sub.n -- to Ar--H ratio was 13:1.
Example 4c
A polymer was prepared by a process as described in Example 4, the
reactants being polyethylene glycol, terephthalic acid and glycerol in the
following amounts and proportions:
______________________________________
Monomer mole mole %
______________________________________
Poly(ethylene glycol) MW 600
0.02 21.74
Dimethyl terephthalate
0.042 45.65
Glycerol 0.03 32.61
______________________________________
The molecular weights were M.sub.n =2500, M.sub.w =5550. The
--(--EO--).sub.n -- to Ar--H ratio was 6.75:1.
Example 5
Preparation of copolymer of poly(ethylene glycol), terephthalic acid,
5-sulphoisophthalic acid sodium salt, glycerol and adipic acid
______________________________________
Reactants g mole mole %
______________________________________
Poly(ethylene glycol) (MW 600)
20.0 0.033 4.85
Dimethyl terephthalate
38.8 0.02 2.94
Dimethyl 5-sulphoisophthalate Na salt
19.8 0.067 9.85
Dimethyl adipate 1.7 0.01 1.47
Glycerol 50.6 0.55 80.88
Antimony trioxide 0.01
Calcium acetate 0.4
Phosphorous acid 0.2
______________________________________
The above ingredients, apart from the phosphorous acid, were charged into a
flanged reactor flask provided with bladed stirrer, thermometer to
register the reactant temperature, O-spot nitrogen inlet, and Claisen
still-head with condenser for the distillation of methanol.
The temperature was first raised to 140.degree.-150.degree. C. (pot
temperature) to melt the solid reactants and thoroughly disperse the
catalyst. The temperature was then raised to 190.degree.-200.degree. C.
and held for 12 hours. Dimethyl terephthalate which sublimed onto the
cooler part of the reactor wall during this stronger heating period, was
periodically remelted back into the teaction. Approximately 25% of the
theoretical amount of methanol distilled up to this stage.
The pre-condensate was then cooled and the phosphorous acid antioxidant in
a little water (0.5 ml) added, before reheating to 240.degree. C. over 4
hours at a vacuum of .about.20 torr. While still molten, the somewhat
cooled reaction mixture was transferred to a Kugelrohr bulb, then heated
to 250.degree. C. at 0.1 torr vacuum for an hour to "complete" the
polycondensation.
The polyester sulphonate thus produced was a fully water-soluble, hard and
brittle resin. It had no recognisable cloud point at 1 wt % in water.
Its apparent molecular weight by aqueous gel permeation chromatography
against polyethylene glycol standards was M.sub.n 7700, M.sub.w 20 300.
The .sup.1 H NMR spectrum (D.sub.2 O) showed major peakes centered at 8.4
and 7.6 ppm assignable to the terephthalate/isophthalate Ar--H's, and at
3.6 ppm assignable to ethyleneoxy groups. Other peaks at around 4.3 ppm
correlated with the glycerol derived chain links.
Example 5a
A sulphonated polymer was prepared as described in Example 5, from the
following monomers in the following amounts and proportions:
______________________________________
Monomers mole mole %
______________________________________
Poly(ethylene glycol) (MW 400)
0.028 3.83
Dimethyl terephthalate
0.20 27.40
Isophthalic acid 0.023 3.15
Dimethyl 5-sulphoisophthalate Na salt
0.012 1.64
Glycerol 0.467 63.97
______________________________________
The molecular weights were M.sub.n =1300, M.sub.w =1800.
Example 5b
A sulphonated polymer was prepared as described in Example 5, from the
following monomers in the following amounts and proportions:
______________________________________
Monomers mole mole %
______________________________________
Poly(ethylene glycol) (MW 400)
0.034 3.83
Dimethyl terephthalate
0.20 22.54
Isophthalic acid 0.028 3.16
Dimethyl 5-sulphoisophthalate Na salt
0.057 6.42
Glycerol 0.568 64.04
______________________________________
The molecular weights were M.sub.n =1500, M.sub.w =1900.
Example 6
Water Solubility
In this Example, the percentage weights of water-soluble and
water-insoluble materials were determined for the polymers of Examples 1,
2, 3 and 4, and for a commercially available polymer, Permalose (Trade
Mark) ex ICI (Comparative Example A). The determination of soluble and
insoluble fractions was carried out by:
preparing a 1 wt % aqueous dispersion of the polymer in water (for
Comparative Example A, by dilution of the commercially available aqueous
dispersion)
stirring the dispersion for two hours,
centrifuging the dispersion for 30 minutes at 25000 revs/min and decanting
the clear layer,
freeze drying and weighing the decanted clear solution (A) and the
dispersed material (B) to determine the percentages of water-soluble
material A*100%/(A+B) and water-insoluble material B*100%/(A+B).
The results were as follows:
______________________________________
Soluble Insoluble
______________________________________
Example 1 100 wt % --
Example 2 100 wt % --
Example 3 100 wt % --
Example 4 100 wt % --
Comparative Example A
63-65 wt %
35-37 wt %
______________________________________
The polymers of Examples 2 and 4 also gave clear solutions at a
concentration of 10 wt %, while the polymer of Example 1 gave a slightly
cloudy solution.
EXAMPLES 7 to 11
Soil Release and Detergency
Example 7
Soil Release
A concentrated powder of the following composition was used to determine
the influence of the soil release polymers of Examples 1 to 3, and a
commercially available PET/POET polymer, Permalose (Trade Mark) ex ICI, on
the removal of triolein from polyester fabric.
______________________________________
%
______________________________________
Primary alkyl sulphate (cocoPAS)
6.13
Nonionic surfactant (7EO)
6.13
Nonionic surfactant (3EO)
7.73
Zeolite MAP (anhydrous basis)
38.47
Hardened tallow soap 2.13
Sodium carbonate 1.05
Sodium carboxymethylcellulose (70%)
0.97
Sodium percarbonate 20.50
TAED (83% granule) 4.75
EDTMP (Dequest (Trade Mark) 2047)
0.37
Enzymes 1.75
Antifoam/fluorescer granule
3.00
Soil release polymer 0 or 1.00
Minor ingredients to 100.00
______________________________________
Soil release was measured using radio-labelled triolein as a soil and
measuring the amount of triolein released into the wash solution by
scintillation counting. Polyester cloths were washed for 20 minutes in the
test formulations (with or without soil release polymer at 1%) at 5 g/l at
40.degree. C. in 24.degree.FH (calcium only) water. The cloths after
rinsing were air dried and then soiled with the radio labelled triolein.
A subsequent wash was carried out under the same conditions as the first
wash and the removal of the triolein measured. This detergency result
shows the soil release benefit for the soil release polymer.
______________________________________
Polymer % Detergency
______________________________________
None 21.6
Permalose 61.3
Example 1 86.6
Example 2 92.4
Example 3 83.0
______________________________________
Example 8
Soil Release
Using the same powder and conditions as in Example 7, three polymers of the
invention were examined, at two different levels (0.5% and 1.0% in the
formulation) for soil release (fabric washed in product, soiled, then
rewashed in product). In these experiments the fabrics were washed in the
test formulations for 20 minutes and then soiled and rewashed in the test
formulation for varying lengths of time.
Results at 0.5 wt % Polymer
______________________________________
No. % triolein removal
Wash time (min)
polymer Ex 1 Ex 2 Ex 4
______________________________________
1 0.92 2.3 7.0 2.8
3 2.21 9.0 26.4 12.0
6 4.11 17.0 43.6 23.4
10 6.20 28.1 52.7 33.7
20 9.78 41.5 66.5 50.8
______________________________________
Results at 1.0 wt % Polymer
______________________________________
No. % triolein removal
Wash time (min)
polymer Ex 1 Ex 2 Ex 4
______________________________________
1 0.92 26.0 25.5 12.8
3 2.21 43.0 44.5 32.9
6 4.11 55.3 57.7 48.5
10 6.20 64.5 67.6 62.2
20 9.78 78.0 80.0 76.5
______________________________________
Further experiments were carried out to show the effect of polymer
concentration in the 20 minute wash:
______________________________________
% triolein removal
% polymer Ex 1 Ex 2 Ex 4
______________________________________
0 9.8 8.9 7.3
0.5 41.5 66.5 50.9
1.0 78.0 80.0 76.5
1.5 76.6 90.0 89.8
2.0 88.5 91.0 88.8
3.0 91.5 90.7 94.5
______________________________________
Example 9
Single Wash Detergency
Experiments were carried out, using the same powder formulation as in
earlier Examples, to determine whether the soil release polymers of
Examples 1a, 1b, 2a, 2b and 4a at 1% had any effect on detergency in a
single wash. The procedure was therefore to soil the cloths and then wash
in the test formulations. For comparison, the commercial polymer Permalose
(Trade Mark) TM (molecular weight 7288) was also tested. The results were
as follows:
______________________________________
Polymer % triolein removal
______________________________________
No polymer 13.7
Permalose 68.4
Example 1a 51.7
Example 1b 57.1
Example 2a 59.4
Example 2b 70.0
Example 4a 64.9
______________________________________
Example 10
Single Wash Detergency
Single-wash detergencies were determined for the polymers of Examples 1, 2
and 4 at various concentrations in the product. Detergency results were as
follows:
Results at 0.5 wt % Polymer
______________________________________
No. % triolein removal
Wash time (min)
polymer Ex 1 Ex 2 Ex 4
______________________________________
1 2.85 3.8 5.3 6.1
3 4.27 8.7 14.5 12.8
6 6.10 16.3 27.4 23.0
10 8.15 24.4 38.8 32.6
20 12.23 36.2 49.0 46.8
______________________________________
Results at 1.0 wt % Polymer
______________________________________
No. % triolein removal
Wash time (min)
polymer Ex 1 Ex 2 Ex 4
______________________________________
1 2.85 4.4 5.0 5.0
3 4.27 11.6 10.7 17.8
6 6.10 20.9 24.6 24.8
10 8.15 28.1 33.6 38.0
20 12.23 41.2 49.5 63.9
______________________________________
Further experiments were carried out to show the effect of polymer
concentration in the 20 minute wash:
______________________________________
% triolein removal
% polymer Ex 1 Ex 2 Ex 4
______________________________________
0 12.2 15.2 13.7
0.3 29.7 44.8 29.1
0.5 36.2 49.0 46.8
1.0 41.2 49.5 63.9
2.0 59.2 72.7 58.5
3.0 63.5 73.2 66.4
______________________________________
Example 11
Soil Release and Detergency
Soil release and single wash detergency were assessed as in previous
Examples, but using a different detergent formulation:
______________________________________
%
______________________________________
Primary alkyl sulphate (cocoPAS)
9.17
Nonionic surfactant (7EO), linear
5.93
Nonionic surfactant (3EO), linear
3.95
Hardened tallow soap 1.55
Zeolite MAP (anhydrous basis)
32.18
Sodium citrate (2aq) 4.25
Sodium carbonate (light)
2.30
Fluorescer 0.05
Sodium carboxymethylcelluose (70%)
0.88
Sodium percarbonate (AvO.sub.2 13.25)
20.50
TAED (83% granule) 6.50
EDTMP (Dequest* 2047) 0.42
Protease (Maxacal* CX600k 2019 GU/mg)
1.50
Lipase (Lipolase* 100T 287 LU/mg)
0.25
Amylase (Termamyl* 60T 4.3 MU/mg)
0.05
Antifoam/fluorescer granule
4.00
Sodium bicarbonate 1.00
Perfume 0.45
Soil release polymer (see below)
0 or 1
Minor ingredients to 100.00
______________________________________
*Trade Mark
The product dosage was 4 g/l. The comparative polymers used were Permalose
(Trade Mark) ex ICI, and Aquaperle (Trade Mark) 3991 ex ICI, both
commercial PET/POET polymers.
______________________________________
Single Wash
Multi-wash
Polymer (soil-wash)
(wash-soil-wash)
______________________________________
No polymer 9.6 9.6
Permalose 59.2 --
Aquaperle 3991 66.9 79.9
Example 1 42.6 44.5
Example 1a 35.4 44.2
Example 2 55.9 72.8
Example 2a 37.7 33.6
Example 2b 63.8 65.3
Example 4 38.1 39.1
Example 4a 49.5 31.3
Example 4c 41.2 35.4
Example 5 71.8 87.7
Example 5a 62.8 83.6
Example 5b 35.2 50.7
______________________________________
The sulphonated polymers of Examples 5 and 5a gave especially good results.
Example 12
Comparative Examples B and C Granular Adjuncts
Granular adjuncts for use in particulate detergent compositions were
prepared by mixing various polymers with sodium sulphate. Where the
polymers were in dilute aqueous solution or dispersion form, the adjuncts
were prepared by adding sodium sulphate to the solution or dispersion,
filtering off solid material, adding excess sodium sulphate, then air
drying at ambient temperature.
Granules were prepared to the following formulations:
______________________________________
Example Polymer Sodium sulphate
______________________________________
12 Polymer of Ex 2a
9.1 90.9
B Permalose 21.8 78.2
C Repel-o-Tex* 50.0 50.0
______________________________________
*Trade Mark, ex RhonePoulenc Chimie
Tergotometer washes were carried out using the formulation and wash regime
of Example 7, the polymer level again being 1 wt %. Results were expressed
as delivery of detergency as a function of time (radio-labelled triolein
removal after a given time, as a percentage of the triolein removal when
the adjunct was fully dissolved). Delivery of detergency was measured
after a single wash, as in Example 9. The results were as follows.
Example % Detergency delivered after
______________________________________
% Detergency delivered after
Example 6 minutes 20 minutes
______________________________________
12 98.5 100.0
B 80.0 96.0
C 89.6 97.0
______________________________________
Example 13
This Example shows the use of a soil release polymer in accordance with the
present invention in a liquid detergent composition:
______________________________________
%
______________________________________
Linear alkylbenzene sulphonate (as acid)
16.5
Nonionic surfactant 7EO
4.5
Nonionic surfactant 3EO
4.5
Oleic-rich fatty acid.sup.1
4.5
Zeolite 4A 15.0
Citric acid 8.23
Potassium hydroxide 10.34
Decoupling polymer.sup.2
1.0
Glycerol 2.0
Borax 1.5
Silicone/silica compound.sup.3
0.3
Perfume 0.5
Fluorescer 0.08
Enzymes 0.91
Soil release polymer 1.00
Water and minor ingredients
to 100.00
______________________________________
.sup.1 PRIOLENE (Trade Mark) 6907 ex Unichema
.sup.2 Narlex (Trade Mark) DC1
.sup.3 DB100 ex Dow Corning
Top